1. Field of the Invention
This invention relates to a process for the removal of organic and/or inorganic pollutants from waste water. More particularly, this invention relates to a process for removal of such pollutants especially substituted and unsubstituted phenols by aerobic biodegradation using a porous biomass support system in a fixed bed reactor.
2. Prior Art
One of the hallmarks of contemporary civilization is that each increment of technological progress almost invariably is accompanied by a similar increment of environmental regress. As the pace of technological advances quickens, so does the march of environmental deterioration. The realization of environmental damage has occurred only relatively recently, so that present society sometimes finds itself burdened with the accumulated sins of the not-too-distant past. But another hallmark of current society is its acceptance of the undesirability of environmental degradation coupled with a determination to minimize and even reverse it wherever possible. Although the return of ground waters to their pristine condition of an earlier era is not a realistic goal, there is a genuine determination to make our waters as pure as possible. Environmental agencies have set limits for many common industrial pollutants, and as methods of pollution, reduction have become more successful in reducing or removing pollutants from waste water, environmental regulations have become more stringent, resulting in an ever tightening spiral whose goal is to reduce pollutants in waste water to that minimum which is technologically feasible.
Among the methods employed to reduce or remove pollutants, bioremediation constitutes an effective and highly desirable approach. Quite broadly, in bioremediation pollutants serve as a food source, generally as a source of carbon and/or nitrogen, for microorganisms. Bacterial metabolism converts the pollutants to metabolites generally with a simple chemical structure, sometimes degrading the pollutants completely to carbon dioxide and water in an aerobic process, or to methane in an anaerobic process. But in any event, the metabolites usually have no adverse environmental effects.
Various bioremediation processes are known. For example, U.S. Pat. No. 4,634,672 describes biologically active compositions for purifying waste water and air which comprises a polyurethane hydrogel containing (i) surface active coal having a specific surface according to BET of above 50 m.sup.2 /g, a polymer having cationic groups and cells having enzymatic activity and being capable of growth. U.S. Pat. No. 4,681,852 describes a process for biological purification of waste water and/or air by contacting the water or air with the biologically active composition of U.S. Pat. No. 4,634,672. The experimental examples of these patents indicate that the process is not effective for reducing contaminant concentrations in the effluent strain to less than 44 parts per million (ppm). This is not acceptable since the Environmental Protection Agency (EPA) in some instances has mandated that concentration for some contaminants (such as phenol) in the effluent stream must be as low as 20 parts-per-billion (ppb). (See Environmental Protection Agency 40 CFR Parts 414 and 416. Organic Chemicals and Plastics and Synthetic Fibers Category Effluent Limitations Guidelines, Pretreatment Standards, and New Source Performance Standards. Federal Register, Vol. 52, No. 214, Thursday, Nov. 5, 1989. Fuels & Regulations, 42522.
Both U.S. Pat. Nos. 3,904,518 and 4,069,148 describe the addition of activated carbon or Fuller's earth to a suspension of biologically active solids (activated sludge) in waste water as an aid in phenol removal. The absorbents presumably act by preventing pollutants toxic to the bacteria from interfering with bacterial metabolic activity. The patentees' approach has matured into the so-called PACT process which has gained commercial acceptance despite its requisites of a long residence time, copious sludge formation with attendant sludge disposal problems, and the need to regenerate and replace spent carbon.
Rehm and coworkers have further refined the use of activated carbon in the aerobic oxidation of phenolic materials by using microorganisms immobilized on granular carbon as a porous biomass support system. Utilizing the propensity of microorganisms to grow on and remain attached to a surface, Rehm used a granular activated carbon support of high surface area (1300 m.sup.2 /g) to Which cells attached within its macropores and on its surface, as a porous biomass support system in a loop reactor for phenol removal. H.M. Ehrhardt and H.J. Rehm, Appl. Microbiol. Biotechnol., 21, 32-6 (1985). The resulting "immobilized" cells exhibited phenol tolerance up to a level in the feed of about 15 g/L, whereas free cells showed a tolerance not more than 1.5 g/L. It was postulated that the activated carbon operated like a "buffer and depot" in protecting the immobilized microorganisms by absorbing toxic phenol concentrations and setting low quantities of the absorbed phenol free for gradual biodegradation. This work was somewhat refined using a mixed culture immobilized on activated carbon [A. Morsen and H.J. Rehm, Appl. Microbiol. Biotechnol., 26, 283- 8 (1987)] where the investigators noted that a considerable amount of microorganisms had "grown out" into the aqueous medium, i.e., there was substantial sludge formation in their system.
Suidan and coworkers have done considerable research on the analogous anaerobic degradation of phenol using a packed bed of microorganisms attached to granular carbon [Y.T. Wang, M.T. Suidan and B.E. Rittman, Journal Water Pollut. Control Fed., 58 227-33 (1986)]. For example, using granular activated carbon of 16.times.20 mesh as a support medium for microorganisms in an expanded bed configuration, and with feed containing from 358-1432 mg phenol/L, effluent phenol levels of about 0.06 mg/L (60 ppb) were obtained at a hydraulic residence time (HRT) of about 24 hours. Somewhat later, a berl-saddle-packed bed and expanded bed granular activated carbon anaerobic reactor in series were used to show a high conversion of COD to methane, virtually all of which occurred in the expanded bed reactor; P.Fox, M.T. Suidan, and J.T. Pfeffer, ibid., 60, 86-92, 1988. The refractory nature of ortho-cresols and meta-cresols toward degradation also was noted.
Givens and Sack, 42nd Purdue University Industrial Waste Conference Proceedings, pp. 93-102 (1987), performed an extensive evaluation of a carbon impregnated polyurethane foam as a microbial support system for the aerobic removal of pollutants, including phenol. Porous polyurethane foam internally impregnated with activated carbon and having microorganisms attached externally was used in an activated sludge reactor, analogous to the Captor and Linpor processes which differ only in the absence of foam-entrapped carbon. The process was attended by substantial sludge formation and without any beneficial effect of carbon.
The Captor process itself utilizes porous polyurethane foam pads to provide a large external surface for microbial growth in an aeration tank for biological waste water treatment. The work described above is the Captor process modified by the presence of carbon entrapped within the foam. A two-year pilot plant evaluation of the Captor process itself showed substantial sludge formation with significantly lower microbial density than had been claimed. J.A. Heidman, R.C. Brenner and H.J. Shah, J. of Environmental Engineering, 114, 1077-96 (1988). A point to be noted, as will be revisited below, is that the Captor process is essentially an aerated sludge reactor where the pads are retained in an aeration tank by screens in the effluent line. Excess sludge needs to be continually removed by removing a portion of the pads via a conveyor and passing the pads through pressure rollers to squeeze out the solids.
H. Bettmann and H.J. Rehm, Appl. Microbial. Biotechnol., 22, 389-393 (1985) have employed a fluidized bed bioreactor for the successful continuous aerobic degradation of phenol at a hydraulic residence time of about 15 hours using Pseudomonas Putida entrapped in a polyacrylamide-hydrazide gel. The use of microorganisms entrapped within polyurethane foams in aerobic oxidation of phenol in shake flasks also has been reported; A.M. Anselmo et al., Biotechnology B.L., 7, 889-894 (1985).
U.S. Pat. No. 2,812,031 relates to the extraction of phenolic materials from aqueous solutions by means of polyurethane foam in the presence of hydrophilic fibers. The patent states that while polyurethane foams are relatively hydrophobic which can interfere with the interfacial contact which is necessary to permit adsorption, the problem is overcome through the use of hydrophilic fibers which enable the materials to come into close and in intimate contact with the surfaces of the polyurethane to facilitate wetting thereof.
U.S. Pat. No. 3,617,531 relates to a method for the selective adsorption of phenol from hydrocarbon solutions. In this method, the solution is contacted with a polyurethane foam.
U.S. Pat. No. 4,469,600 describes the biological purification of wastewater in the presence of an open-pore and compressible carrier material for the biomass. U.S. Pat. No. 4,461,708 describes a process for purifying effluent waters, particularly those produced in the wood-processing industry, through use of a fluidized reactor containing finely divided particles and agglomerated fiber material serving the purpose of reducing the quantity of floating particles. U.S. Pat. No. 3,933,629 discloses the biological treatment of an aqueous effluent stream with a filler unit having lower sand layer, an intermediate anthracite layer and a polystyrene layer. U.S. Pat. No. 4,561,974 discloses an apparatus for the anaerobic filtration of waste water which includes a filter of a filling material or the apparatus having a lower layer of a filling material in the form of an ordered arrangement of material, and having upper and intermediate layers, each include a loosely packed arrangement of material thereof.
U.S. Pat. No. 4,589,927 discloses liquid multisolid fluidized bed processing by a liquid fluidized bed reactor in which improved mixing and mass transport between gas/liquid/solid phases is provided by fluidizing large particles in the bottom of the reactor while recirculating small enhanced particles and the liquid through the reactor.
U.S. Pat. No. 4,983,299 and PCT WO 90/11970 describe fixed bed reactors for the bioremediation or organic contaminants where the reactor contains a biomass formed from particles having a substrate such as polyurethane foam having anaerobic microbes and an absorbent for the pollutant on, in or on all in said substrate.
U.S. Pat. No. 4,165,281 discloses a method and a unit for wastewater treatment with microorganisms, in which at least one non-woven fibrous mat having a three-dimensional network structure is disposed as a supporting media in an aeration tank, microorganisms are retained on the surface of and in the interstices of the non-woven fibrous mat, and organic polluting matter in the wastewater is oxidatively decomposed by the microorganisms in the presence of oxygen.
U.S. Pat. No. 4,820,415 discloses a process for the biological treatment of an aqueous waste containing liquid by the removal of organic matter by microorganisms wherein a carrier material for said microorganisms is added to said liquid and wherein said carrier material comprises a filler-containing, hydrophilic, open-celled polymer in the form of separate individual particles, the improvement wherein said polymer particles, when saturated with water and charged with at least 70 volume % of biomass formed in the course of the process, have an average density of slightly below the density of said liquid and thereby are suspended in the upper two-thirds of said liquid.
U.S. Pat. No. 4,469,600 describes the biological purification of wastewater in a reactor in the presence of open-pore and compressible carrier material for biomass, the carrier material, prior to its use in the reactor, is loaded with bacteria, finely divided, inorganic and/or organic compounds, selected for wastewater purification, and is then either stored or used in the process, the loaded carrier being especially useful for decreasing the start-up time of a wastewater treatment plant.
U.S. Pat. No. 4,576,718 relates to the use of non-floating, non-abrasive, highly-filled polyurethane (urea) compositions of high water-absorbability, which during their production contain no cells capable of growth as carriers for biomass in the biological treatment of waste containing liquids. These carriers have a filler content of greater than 15% by weight and less than 95% by weight (based on the moisture-free). The fillers are selected from the group consisting of natural materials containing finely-divided fossil lignocellulose or the secondary products thereof (e.g., peat, lignite, mineral coal or coke), active carbon, finely-divided distillation residues, inorganic fillers, homogeneous or cellular plastics particles (and more particularly polyurethane foam (waste) particles) and mixtures thereof. The polyurethane (urea) is a hydrophilic and/or hydrophobic polyurethane(urea), and preferably contains cationic groups. These highly-filled, polyurethane (urea) carriers have a water-absorbability exceeding 33% by weight of water in the swollen carrier.
U.S Pat. No. 5,037,551 discloses a method and an apparatus for dehalogenation and further biodegrading organic compounds, including halogenated organic compounds, present in an aqueous mixture, the mixture comprising the waste effluent produced in a continuous high flow rate by an industrial plant such as a bleach pulp or paper mil using chlorine and chlorine compounds. The aqueous mixture is passed through at least one combination of a first oxygen-enriched liquid zone and a second zone containing a mixed population of methanotrophic and heterotrophic microorganisms supported on a substrate bed. A first gas including oxygen is flowed through the first zone and second gas consisting substantially of a low-molecular-weight alkane is flowed through the second zone as the aqueous mixture passes through the first and second zones. The microorganisms supported by the bed dehalogenated and further biodegrade the organic compounds in the aqueous liquid flowing through the bed as they aerobically metabolize the low-molecular-weight alkane. The first zone may be hydraulically coupled to an upstream aerobic biopond for decreasing the total organic carbon and biochemical oxygen demand of the aqueous mixture before the mixture is passed through the first and second zones. A plurality of paired first and second zones may be hydraulically interconnected to achieve a higher degree of dehalogenation and further biodegradation of organic compounds in the aqueous mixture flowing therethrough and/or to accommodate higher flow rate.